US4374943A - Polysulfide alkoxy silane coupling agents - Google Patents
Polysulfide alkoxy silane coupling agents Download PDFInfo
- Publication number
- US4374943A US4374943A US06/228,947 US22894781A US4374943A US 4374943 A US4374943 A US 4374943A US 22894781 A US22894781 A US 22894781A US 4374943 A US4374943 A US 4374943A
- Authority
- US
- United States
- Prior art keywords
- radical
- value
- carbon atoms
- polysulfide
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Definitions
- This invention relates to sulfur vulcanizable elastomer composites which are based upon vulcanizable unsaturated polymers and copolymers such as natural rubbers, polyisoprenes, polybutadienes, poly(butadiene-co-styrene), poly(butadiene-co-acrylontrile), poly(isobutylene-co-butadiene, and the like. More particularly, this invention relates to means for enhancing the coupling action, in such sulfur vulcanizable elastomers, of polysulfide alkoxy silane coupling agents.
- Polysulfide alkoxy silane coupling agents are known, and are described e.g. in U.S. Pat. Nos. 3,842,111, 3,873,489, 4,003,843, and 4,044,037.
- Polysulfide-functional organosilanes are, like mercapto-functional organosilanes, useful as coupling agents in silica-filled and silicate-filled sulfur vulcanizable elastomer composites.
- the polysulfide-functional organosilanes are, as compared to the mercapto-functional organosilanes, less active. Under comparable conditions, the former produce lesser improvements than do the latter in elastomer vulcanizate properties such as tensile modulus.
- triorganophosphines can be utilized to enhance the coupling action of polysulfide alkoxy silane coupling agents. More specifically, it has been found that compositions which contain triorganophosphine (preferably in admixture with water, lower alkanol, and porous inert inorganic solid carrier) can be utilized to enhance the coupling action of polysulfide alkoxy silane coupling agents in the preparation of vulcanizable rubber from formulations comprising a major proportion of vulcanizable unsaturated polymer or copolymer and a small amount of polysulfide alkoxy silane coupling agent.
- compositions which contain a polysulfide alkoxy silane coupling agent and a triorganophosphine, can be utilized in the vulcanization of sulfur-vulcanizable formulations containing a major proportion of vulcanizable unsaturated polymer or copolymer.
- the utilization of such compositions improves the elastomer vulcanizate properties as compared to the use of similar compositions without the triorganophosphine.
- the sulfur-vulcanizable elastomer composites in which improved coupling action according to the present invention can be obtained are those based upon unsaturated polymers and copolymers such as natural rubbers, polyisoprenes, polybutadienes, (poly(butadiene-co-styrene), poly(butadiene-co-acrylonitrile), poly(isobutylene-co-butadiene), and the like.
- the preferred sulfur-vulcanizable elastomer composites are those based upon styrene-butadiene copolymers.
- polysulfide alkoxy silane coupling agents which can be employed according to the present invention are known as a class and are described, for example in U.S. Pat. Nos. 3,842,111, 3,873,489, 4,003,843, and 4,044,037.
- a preferred variety of these coupling agents is represented by the formula ##STR1## wherein X represents an alkoxy radical, R' represents an alkyl radical having up to four carbon atoms, y has a value of from 0 to 2 inclusive, R represents a divalent bridging group selected from the group consisting of alkylene and alkyleneoxy radicals having up to seven carbon atoms, n has a value of 0 or 1, p has a value of 0 or 1, Ar represents an aryl radical containing from 6 to 12 carbon atoms, (S) x represents a divalent polysulfide radical each free valence thereof being directly bonded to an aromatic carbon atom of an Ar radical whereby each Ar radical is bonded to another Ar radical through a (S) x radical, x has a value of from 2 to 6, a has a value of at least 2, b has a value of at least 1, and the ratio of a to b is a value of not more than 2.
- Illustrative of this preferred variety of coupling agents are the silanes having the formulae [(CH 3 O) 3 Si(CH 2 ) 3 ] 2 [S x ] wherein x has an average value of about 4, [(CH 3 O) 3 Si(CH 2 ) 3 ] 2 [S 2 ], and ##STR2## where y has an average value of about 3.
- the latter silane is most preferred.
- organophosphines which can be used according to the present invention are those of the formula R 1 R 2 R 3 P, wherein each R represents an organo radical.
- the preferred organo radicals are alkyl radicals, especially those having up to eight carbon atoms.
- Exemplary organophosphines include trimethylphosphine, triethylphosphine, triisopropylphosphine, triheptylphosphine, etc.
- the most preferred organophosphine is tri-n-butylphosphine.
- the organophosphine additive is conveniently utilized in the form of a dry concentrate.
- a dry concentrate is to stir the organophosphine and water in a low alkanol, e.g. methanol solvent for a few minutes at room temperature, and then to take up the liquid on a porous inert inorganic solid, e.g. calcium silicate, carrier to form a dry concentrate.
- the dry concentrate can then be added to sulfur-vulcanizable rubber formulations which contain polysulfide silane coupling agent.
- Another approach is to stir the polysulfide silane coupling agent as well as the organophosphine and water in a lower alkanol, e.g.
- methanol methanol, solvent for a few minutes at room temperature, and again to take up the liquid on a porous inert inorganic solid, e.g. calcium silicate, carrier to form a dry concentrate.
- Said dry concentrate can then be added to sulfur-vulcanizable rubber formulations. It is believed that the water supplies protons which reduce the polysulfide linkages. The amount of water utilized will be that necessary to obtain the desired rubber curing rate.
- a typical elastomer base contains 100 parts by weight of SBR 1502, a styrene-butadiene copolymer (as described in "The Elastomers Manual", International Institute of Synthetic Rubber Producers, 1974 Edition, page 22), 50 parts by weight of precipitated high surface area silica, 8 parts by weight of aromatic hydrocarbon oil, 1.0 parts by weight of tetramethylthiuram monosulfide, 1.5 parts by weight of 2-mercaptobenzothiazole, 2.0 parts by weight of sulfur, 5.0 parts by weight of zinc oxide, 1.0 part by weight of stearic acid, and varying parts by weight of additives according to the present invention.
- the elastomer base is processed as follows: The SBR 1502 is banded on a two-roll 6" ⁇ 12" laboratory rubber mill at a roll temperature of 125° F. and is milled for one minute, dry concentrates according to the present invention are added and dispersed by further milling for about two minutes, half of the silica filler are added followed by the addition of the remaining half along with the aromatic hydrocarbon oil, and these components are dispersed by further milling for two to three minutes, at which time the remaining (vulcanizing) chemicals is added and dispersed; the mixture so-obtained is removed from the mill as a sheet and is press-vulcanized at 320° F. to form ASTM tensile test sheets. Physical tests of the vulcanizate were performed according to standard ASTM test methods.
- Tensile Modulus Evidence of action by a coupling agent in a composite is manifested through changes in composite physical property values away from the values displayed by the composite in the absence of the agent.
- Composite properties which may be favorably altered by coupling agent action are many and varied. For example, in elastomeric composites, the effects of coupling agents are seen in terms of increased tensile modulus and abrasion resistance and in decreased hysteresis losses in flexure. In highly extensible elastomeric composites, the measurement of changes in tensile modulus is a particularly useful way of observing coupling effects and has been used extensively in the experimental work described herein.
- Tensile modulus is defined here as the tensile stress in pounds per square inch of original cross-sectional area necessary to produce a selected extension in a composite specimen, usually 100%, 200%, or 300% of the unstressed length; these parameters are usually indicated as M100, M200, or M300, respectively.
- organophosphine according to the present invention results in a significant and unexpected increase in the tensile moduli (e.g., M100 and M300) of vulcanizates embodying it.
- organophosphine according to the present invention results in a significant increase in the tensile moduli (e.g., M100 and M300) of vulcanizates embodying it.
Abstract
The coupling action of polysulfide alkoxy silanes in rubbers is enhanced by the utilization of triorganophosphine compositions.
Description
This is a continuation-in-part of U.S. patent application Ser. No. 079,499, which was filed on Sept. 27, 1979 and is now abandoned.
1. Field of the Invention
This invention relates to sulfur vulcanizable elastomer composites which are based upon vulcanizable unsaturated polymers and copolymers such as natural rubbers, polyisoprenes, polybutadienes, poly(butadiene-co-styrene), poly(butadiene-co-acrylontrile), poly(isobutylene-co-butadiene, and the like. More particularly, this invention relates to means for enhancing the coupling action, in such sulfur vulcanizable elastomers, of polysulfide alkoxy silane coupling agents.
2. Description of the Prior Art
Polysulfide alkoxy silane coupling agents are known, and are described e.g. in U.S. Pat. Nos. 3,842,111, 3,873,489, 4,003,843, and 4,044,037. Polysulfide-functional organosilanes are, like mercapto-functional organosilanes, useful as coupling agents in silica-filled and silicate-filled sulfur vulcanizable elastomer composites. However, the polysulfide-functional organosilanes are, as compared to the mercapto-functional organosilanes, less active. Under comparable conditions, the former produce lesser improvements than do the latter in elastomer vulcanizate properties such as tensile modulus.
It has now been found that triorganophosphines can be utilized to enhance the coupling action of polysulfide alkoxy silane coupling agents. More specifically, it has been found that compositions which contain triorganophosphine (preferably in admixture with water, lower alkanol, and porous inert inorganic solid carrier) can be utilized to enhance the coupling action of polysulfide alkoxy silane coupling agents in the preparation of vulcanizable rubber from formulations comprising a major proportion of vulcanizable unsaturated polymer or copolymer and a small amount of polysulfide alkoxy silane coupling agent. Also, it has been found that compositions which contain a polysulfide alkoxy silane coupling agent and a triorganophosphine, (preferably in admixture with water, lower alkanol, and porous inert inorganic solid) can be utilized in the vulcanization of sulfur-vulcanizable formulations containing a major proportion of vulcanizable unsaturated polymer or copolymer. The utilization of such compositions improves the elastomer vulcanizate properties as compared to the use of similar compositions without the triorganophosphine.
The sulfur-vulcanizable elastomer composites in which improved coupling action according to the present invention can be obtained are those based upon unsaturated polymers and copolymers such as natural rubbers, polyisoprenes, polybutadienes, (poly(butadiene-co-styrene), poly(butadiene-co-acrylonitrile), poly(isobutylene-co-butadiene), and the like. The preferred sulfur-vulcanizable elastomer composites are those based upon styrene-butadiene copolymers.
The polysulfide alkoxy silane coupling agents which can be employed according to the present invention are known as a class and are described, for example in U.S. Pat. Nos. 3,842,111, 3,873,489, 4,003,843, and 4,044,037. A preferred variety of these coupling agents is represented by the formula ##STR1## wherein X represents an alkoxy radical, R' represents an alkyl radical having up to four carbon atoms, y has a value of from 0 to 2 inclusive, R represents a divalent bridging group selected from the group consisting of alkylene and alkyleneoxy radicals having up to seven carbon atoms, n has a value of 0 or 1, p has a value of 0 or 1, Ar represents an aryl radical containing from 6 to 12 carbon atoms, (S)x represents a divalent polysulfide radical each free valence thereof being directly bonded to an aromatic carbon atom of an Ar radical whereby each Ar radical is bonded to another Ar radical through a (S)x radical, x has a value of from 2 to 6, a has a value of at least 2, b has a value of at least 1, and the ratio of a to b is a value of not more than 2. Illustrative of this preferred variety of coupling agents are the silanes having the formulae [(CH3 O)3 Si(CH2)3 ]2 [Sx ] wherein x has an average value of about 4, [(CH3 O)3 Si(CH2)3 ]2 [S2 ], and ##STR2## where y has an average value of about 3. The latter silane is most preferred.
The organophosphines which can be used according to the present invention are those of the formula R1 R2 R3 P, wherein each R represents an organo radical. The preferred organo radicals are alkyl radicals, especially those having up to eight carbon atoms. Exemplary organophosphines include trimethylphosphine, triethylphosphine, triisopropylphosphine, triheptylphosphine, etc. The most preferred organophosphine is tri-n-butylphosphine.
The organophosphine additive is conveniently utilized in the form of a dry concentrate. One approach is to stir the organophosphine and water in a low alkanol, e.g. methanol solvent for a few minutes at room temperature, and then to take up the liquid on a porous inert inorganic solid, e.g. calcium silicate, carrier to form a dry concentrate. The dry concentrate can then be added to sulfur-vulcanizable rubber formulations which contain polysulfide silane coupling agent. Another approach is to stir the polysulfide silane coupling agent as well as the organophosphine and water in a lower alkanol, e.g. methanol, solvent for a few minutes at room temperature, and again to take up the liquid on a porous inert inorganic solid, e.g. calcium silicate, carrier to form a dry concentrate. Said dry concentrate can then be added to sulfur-vulcanizable rubber formulations. It is believed that the water supplies protons which reduce the polysulfide linkages. The amount of water utilized will be that necessary to obtain the desired rubber curing rate.
The specific examples which follow are illustrative of the principles of the invention.
Elastomer Base: A typical elastomer base contains 100 parts by weight of SBR 1502, a styrene-butadiene copolymer (as described in "The Elastomers Manual", International Institute of Synthetic Rubber Producers, 1974 Edition, page 22), 50 parts by weight of precipitated high surface area silica, 8 parts by weight of aromatic hydrocarbon oil, 1.0 parts by weight of tetramethylthiuram monosulfide, 1.5 parts by weight of 2-mercaptobenzothiazole, 2.0 parts by weight of sulfur, 5.0 parts by weight of zinc oxide, 1.0 part by weight of stearic acid, and varying parts by weight of additives according to the present invention.
The elastomer base is processed as follows: The SBR 1502 is banded on a two-roll 6"×12" laboratory rubber mill at a roll temperature of 125° F. and is milled for one minute, dry concentrates according to the present invention are added and dispersed by further milling for about two minutes, half of the silica filler are added followed by the addition of the remaining half along with the aromatic hydrocarbon oil, and these components are dispersed by further milling for two to three minutes, at which time the remaining (vulcanizing) chemicals is added and dispersed; the mixture so-obtained is removed from the mill as a sheet and is press-vulcanized at 320° F. to form ASTM tensile test sheets. Physical tests of the vulcanizate were performed according to standard ASTM test methods.
Tensile Modulus: Evidence of action by a coupling agent in a composite is manifested through changes in composite physical property values away from the values displayed by the composite in the absence of the agent. Composite properties which may be favorably altered by coupling agent action are many and varied. For example, in elastomeric composites, the effects of coupling agents are seen in terms of increased tensile modulus and abrasion resistance and in decreased hysteresis losses in flexure. In highly extensible elastomeric composites, the measurement of changes in tensile modulus is a particularly useful way of observing coupling effects and has been used extensively in the experimental work described herein. Tensile modulus is defined here as the tensile stress in pounds per square inch of original cross-sectional area necessary to produce a selected extension in a composite specimen, usually 100%, 200%, or 300% of the unstressed length; these parameters are usually indicated as M100, M200, or M300, respectively.
In this Example, additives compositions as indicated were added to the Elastomer Base described above (the values given are in parts per 100 parts SBR 1502):
______________________________________
Additive 1 2 3 4
______________________________________
##STR3## 0 1.5 1.5 1.5
Tri-n-butylphosphine
0 0 0 1.8
Microporous Synthetic Calcium
0 0 3.5 3.5
Silicate
Methanol 0 0 3.0 3.0
Water 0 0 0.2 0.2
______________________________________
The ASTM test results were ("ppsi"=pounds per square inch):
______________________________________
Vulcanizate 1 2 3 4
______________________________________
Hardness (Shore A)
60 60 60 65
M100 (ppsi) 125 175 175 225
M300 (ppsi) 250 500 500 1000
Tensile (ppsi)
2200 3100 3000 2200
Elongation (%)
1000 800 800 500
C Tear (ppsi)
200 300 300 300
______________________________________
It is evident that the use of an organophosphine according to the present invention results in a significant and unexpected increase in the tensile moduli (e.g., M100 and M300) of vulcanizates embodying it.
In this Example, 1.5 parts per 100 parts SBR 1502 of a polysulfide silane coupling agent, ##STR4## was added to the Elastomer Base described above (except in the Control Run, 1) prior to the addition of the indicated amounts of the other additives (the values given are in parts per 100 parts SBR 1502):
______________________________________
Additive 1 2 3 4 5 6 7
______________________________________
Tri-n-butylphos-
0 0 0.4 0.8 1.2 1.6 2.0
phine
Microporus Syn-
0 0 0.4 0.8 1.2 1.6 2.0
thetic Calcium
Silicate
Methanol 0 0 0.38 0.76 1.14 1.52 1.90
Water 0 0 0.01 0.04 0.06 0.08 0.10
______________________________________
The ASTM test results were ("ppsi"=pounds per square inch):
______________________________________
Vulcanizate 1 2 3 4 5 6 7
______________________________________
Hardness (Shore A)
60 65 65 65 65 65 70
M100 (ppsi) 125 200 225 225 250 275 275
M300 (ppsi) 250 600 700 800 950 900 900
Tensile (ppsi)
2200 2900 2700 2500 2400 2200 2200
Elongation (%)
1000 700 650 600 550 550 550
C Tear (ppsi)
200 300 300 300 300 300 300
______________________________________
It is again evident that the use of an organophosphine according to the present invention results in a significant increase in the tensile moduli (e.g., M100 and M300) of vulcanizates embodying it.
Various modifications and variations of these illustrative Examples will be obvious to those workers skilled in the art. Such modifications and variations are included with the purview of this invention and are encompassed by the scope and spirit of the appended claims.
Claims (7)
1. A dry concentrate which comprises (I) a triorganophosphine of the formula R1 R2 R3 P, wherein each of R1, R2, and R3 represents an alkyl radical having up to eight carbon atoms, (II) water, (III) lower alkanol, and (IV) porous inert inorganic solid.
2. A dry concentrate which comprises (I) a polysulfide alkoxysilane coupling agent of the formula ##STR5## wherein X represents an alkoxy radical, R' represents an alkyl radical having up to four carbon atoms, y has a value of from 0 to 2 inclusive, R represents a divalent bridging group selected from the group consisting of alkylene and alkyleneoxy radicals having up to seven carbon atoms, n has a value of 0 or 1, p has a value of 0 or 1, Ar represents an aryl radical containing from 6 to 12 carbon atoms, (S)x represents a divalent polysulfide radical each free valence thereof being directly bonded to an aromatic carbon atom of an Ar radical whereby each Ar radical is bonded to another Ar radical through a (S)x radical, x has a value of from 2 to 6, a has a value of at least 2, b has a value of at least 1, and the ratio of a to b is a value of not more than 2, (II) a triorganophosphine of the formula R1 R2 R3 P, wherein each of R1, R2, and R3 represents an alkyl radical having up to eight carbon atoms, (III) water, (IV) lower alkanol, and (V) porous inert inorganic solid.
3. A composition as in claim 2 wherein the polysulfide silane coupling agent is that of the formula ##STR6##
4. A composition as in claim 1 or 2 in which the triorganophosphine is that of the formula
(n-C.sub.4 H.sub.9).sub.3 P
5. A sulphur vulcanizable formulation which comprises a major proportion of vulcanizable unsaturated polymer or copolymer selected from the group consisting of natural rubbers, polyisoprenes, polybutadienes, poly(isobutylene-co-butadiene), poly(butadiene-co-acrylonitrile) and poly(butadiene-co-styrene) and which contains a composition as in claim 1 or 2.
6. A process for preparing a vulcanized rubber which comprises vulcanizing the formulation of claim 5.
7. The product of the process of claim 6.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/228,947 US4374943A (en) | 1979-09-27 | 1981-01-27 | Polysulfide alkoxy silane coupling agents |
| CA000393899A CA1193034A (en) | 1981-01-27 | 1982-01-11 | Triorgano phosphines useful in enhancing polysulfide alkoxy silane coupling agents |
| DE8282100520T DE3263331D1 (en) | 1981-01-27 | 1982-01-26 | The use of triorganophosphines for improving the effectivity of polysulphide alkoxysilane coupling agents |
| JP57009642A JPS57145135A (en) | 1981-01-27 | 1982-01-26 | Dry concentrated matter |
| AU79839/82A AU7983982A (en) | 1981-01-27 | 1982-01-26 | Coupling agent |
| EP82100520A EP0057013B1 (en) | 1981-01-27 | 1982-01-26 | The use of triorganophosphines for improving the effectivity of polysulphide alkoxysilane coupling agents |
| SG696/86A SG69686G (en) | 1981-01-27 | 1986-08-25 | The use of triorganophosphines for improving the effectivity of polysulphide alkoxysilane coupling |
| HK80/88A HK8088A (en) | 1981-01-27 | 1988-01-28 | The use of triorganophosphines for improving the effectivity of polysulphide alkoxysilane coupling agents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7949979A | 1979-09-27 | 1979-09-27 | |
| US06/228,947 US4374943A (en) | 1979-09-27 | 1981-01-27 | Polysulfide alkoxy silane coupling agents |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US7949979A Continuation-In-Part | 1979-09-27 | 1979-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4374943A true US4374943A (en) | 1983-02-22 |
Family
ID=22859208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/228,947 Expired - Lifetime US4374943A (en) | 1979-09-27 | 1981-01-27 | Polysulfide alkoxy silane coupling agents |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4374943A (en) |
| EP (1) | EP0057013B1 (en) |
| JP (1) | JPS57145135A (en) |
| AU (1) | AU7983982A (en) |
| CA (1) | CA1193034A (en) |
| DE (1) | DE3263331D1 (en) |
| HK (1) | HK8088A (en) |
| SG (1) | SG69686G (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504551A (en) * | 1983-04-28 | 1985-03-12 | Phillips Petroleum Company | Poly(arylene sulfide) compositions |
| US5218015A (en) * | 1989-10-06 | 1993-06-08 | Somar Corporation | Hardening agent composition, method of preparing the same and thermosetting epoxy resin composition based on surface treated zeolites |
| US6015870A (en) * | 1997-09-26 | 2000-01-18 | Shin-Etsu Chemical Co., Ltd. | Process for preparing polysulfide silanes |
| EP1172405A1 (en) * | 2000-07-14 | 2002-01-16 | The Goodyear Tire & Rubber Company | Rubber compositions containing a trivalent phosphorous compound-silica complex |
| US20050180721A1 (en) * | 2004-02-06 | 2005-08-18 | Seiko Epson Corporation | Method for manufacturing electro-optic device, electro-optic device, and electronic apparatus |
| US20110184087A1 (en) * | 2007-10-19 | 2011-07-28 | Lanxess Inc. | Butyl rubber compounds comprising a mixed modifier system |
| US11535687B2 (en) | 2011-10-24 | 2022-12-27 | Bridgestone Americas Tire Operations, Llc | Silica-filled rubber composition and method for making the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3388531B2 (en) * | 1996-11-29 | 2003-03-24 | 信越化学工業株式会社 | Method for desulfurizing polysulfide silane |
| DE19858863A1 (en) * | 1998-12-19 | 2000-06-21 | Degussa | Rubber compounds containing organosilane polysulfanes |
| MX2018002513A (en) | 2015-08-28 | 2018-06-11 | Arlanxeo Deutschland Gmbh | Increased efficiency desulfurization reagents. |
| EP3135712A1 (en) | 2015-08-28 | 2017-03-01 | ARLANXEO Deutschland GmbH | Increased efficiency of desulfurization reagents |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072618A (en) * | 1959-04-01 | 1963-01-08 | Exxon Research Engineering Co | Sulfonation with organic phosphorous compound-sulfur trioxide adducts |
| US3697620A (en) * | 1970-04-22 | 1972-10-10 | American Cyanamid Co | Vulcanizable elastomer composition containing triarylphosphine and triallylcyanurate |
| US3752787A (en) * | 1972-01-28 | 1973-08-14 | Du Pont | Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator |
| US3842111A (en) * | 1971-08-17 | 1974-10-15 | Degussa | Sulfur containing organosilicon compounds |
| US3873489A (en) * | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| US3962179A (en) * | 1974-12-19 | 1976-06-08 | E. I. Du Pont De Nemours And Company | Neoprene compositions containing triarylphosphines |
| US4003843A (en) * | 1974-06-21 | 1977-01-18 | Bayer Aktiengesellschaft | Vulcanization systems for rubber mixtures with light fillers |
| US4044037A (en) * | 1974-12-24 | 1977-08-23 | Union Carbide Corporation | Sulfur containing silane coupling agents |
-
1981
- 1981-01-27 US US06/228,947 patent/US4374943A/en not_active Expired - Lifetime
-
1982
- 1982-01-11 CA CA000393899A patent/CA1193034A/en not_active Expired
- 1982-01-26 EP EP82100520A patent/EP0057013B1/en not_active Expired
- 1982-01-26 JP JP57009642A patent/JPS57145135A/en active Granted
- 1982-01-26 DE DE8282100520T patent/DE3263331D1/en not_active Expired
- 1982-01-26 AU AU79839/82A patent/AU7983982A/en not_active Abandoned
-
1986
- 1986-08-25 SG SG696/86A patent/SG69686G/en unknown
-
1988
- 1988-01-28 HK HK80/88A patent/HK8088A/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072618A (en) * | 1959-04-01 | 1963-01-08 | Exxon Research Engineering Co | Sulfonation with organic phosphorous compound-sulfur trioxide adducts |
| US3697620A (en) * | 1970-04-22 | 1972-10-10 | American Cyanamid Co | Vulcanizable elastomer composition containing triarylphosphine and triallylcyanurate |
| US3842111A (en) * | 1971-08-17 | 1974-10-15 | Degussa | Sulfur containing organosilicon compounds |
| US3873489A (en) * | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| US3752787A (en) * | 1972-01-28 | 1973-08-14 | Du Pont | Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator |
| US4003843A (en) * | 1974-06-21 | 1977-01-18 | Bayer Aktiengesellschaft | Vulcanization systems for rubber mixtures with light fillers |
| US3962179A (en) * | 1974-12-19 | 1976-06-08 | E. I. Du Pont De Nemours And Company | Neoprene compositions containing triarylphosphines |
| US4044037A (en) * | 1974-12-24 | 1977-08-23 | Union Carbide Corporation | Sulfur containing silane coupling agents |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504551A (en) * | 1983-04-28 | 1985-03-12 | Phillips Petroleum Company | Poly(arylene sulfide) compositions |
| US5218015A (en) * | 1989-10-06 | 1993-06-08 | Somar Corporation | Hardening agent composition, method of preparing the same and thermosetting epoxy resin composition based on surface treated zeolites |
| US6015870A (en) * | 1997-09-26 | 2000-01-18 | Shin-Etsu Chemical Co., Ltd. | Process for preparing polysulfide silanes |
| EP1172405A1 (en) * | 2000-07-14 | 2002-01-16 | The Goodyear Tire & Rubber Company | Rubber compositions containing a trivalent phosphorous compound-silica complex |
| US6441070B1 (en) | 2000-07-14 | 2002-08-27 | The Goodyear Tire & Rubber Company | Rubber compositions containing a trivalent phosphorous compound-silica complex |
| US20050180721A1 (en) * | 2004-02-06 | 2005-08-18 | Seiko Epson Corporation | Method for manufacturing electro-optic device, electro-optic device, and electronic apparatus |
| US20110184087A1 (en) * | 2007-10-19 | 2011-07-28 | Lanxess Inc. | Butyl rubber compounds comprising a mixed modifier system |
| US11535687B2 (en) | 2011-10-24 | 2022-12-27 | Bridgestone Americas Tire Operations, Llc | Silica-filled rubber composition and method for making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7983982A (en) | 1982-08-05 |
| EP0057013A2 (en) | 1982-08-04 |
| JPS57145135A (en) | 1982-09-08 |
| JPH0216771B2 (en) | 1990-04-18 |
| EP0057013A3 (en) | 1982-08-25 |
| CA1193034A (en) | 1985-09-03 |
| DE3263331D1 (en) | 1985-06-05 |
| SG69686G (en) | 1987-02-27 |
| HK8088A (en) | 1988-02-05 |
| EP0057013B1 (en) | 1985-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1136309A (en) | Silicate-filled vulcanizable halogen rubber mixtures | |
| US4002594A (en) | Scorch retardants for rubber reinforced with siliceous pigment and mercapto-type coupling agent | |
| EP0670347B1 (en) | Rubber compositions containing reinforcing additives which contain sulfur and silicon | |
| CA1161185A (en) | Vulcanizable rubber mixture containing an organosilane | |
| US6268421B1 (en) | Reinforcement additives | |
| DE60126135T3 (en) | Elastomeric compositions containing inorganic fillers | |
| US4374943A (en) | Polysulfide alkoxy silane coupling agents | |
| DE10354616A1 (en) | rubber compounds | |
| PL87778B1 (en) | ||
| EP0192930A1 (en) | Natural rubber containing compositions with increased tear strength | |
| DE69836722T2 (en) | rubber composition | |
| DE2933247A1 (en) | Vulcanisable rubber mixt. having low residual pressure deformation - contains rubber, a silane, polysiloxane and/or poly:silazane, silica filler and crosslinking agent | |
| CA1150291A (en) | Silane reinforcing promoters in reinforcement of silica filled rubbers | |
| DE4128203C1 (en) | ||
| CA1291284C (en) | Elastomeric composition having improved cut growth resistance | |
| EP0744437A1 (en) | Mixtures of organosilane compounds and their use | |
| KR910009837A (en) | Stabilizer Mixtures for Elastomers | |
| US20030144393A1 (en) | Functionalised silane-based compounds, methods for producing them and their use in the area of rubber materials | |
| US4426480A (en) | Organo siloxanes, method for the preparation thereof and polymeric compositions containing same | |
| EP0090382A2 (en) | Organo siloxanes, method for the preparation thereof and polymeric compositions containing same | |
| US6087424A (en) | Rubber composition | |
| DE4100217A1 (en) | WITH PEROXIDE VULCANIZABLE MOLDING AND A METHOD OF MANUFACTURING | |
| US4324870A (en) | Scorch-safe acceleration of urethane vulcanization of unsaturated rubbers | |
| DE4233197A1 (en) | New vulcanization accelerators suitable for the introduction of polar substituents | |
| CA1124426A (en) | Siliceous filler-silane-stabiliser composition for polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, 270 PARK AVENUE, NEW YO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:WILLIAMS THOMAS C.;REEL/FRAME:003849/0467 Effective date: 19810403 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| AS | Assignment |
Owner name: MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MOR Free format text: MORTGAGE;ASSIGNORS:UNION CARBIDE CORPORATION, A CORP.,;STP CORPORATION, A CORP. OF DE.,;UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,;AND OTHERS;REEL/FRAME:004547/0001 Effective date: 19860106 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
| AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MORGAN BANK (DELAWARE) AS COLLATERAL AGENT;REEL/FRAME:004665/0131 Effective date: 19860925 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |
|
| AS | Assignment |
Owner name: CHASE MANHATTAN BANK (N.A.), NEW YORK Free format text: SECURITY INTEREST;ASSIGNOR:OSI, SPECIALTIES, INC.;REEL/FRAME:006624/0803 Effective date: 19930708 Owner name: OSI SPECIALTIES, INC. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNION CARBIDE CHEMICALS AND PLASTICS CORP.;REEL/FRAME:006633/0206 Effective date: 19930709 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |